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CN102176819A - Synergistic rodenticidal agent - Google Patents

Synergistic rodenticidal agent Download PDF

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Publication number
CN102176819A
CN102176819A CN2009801405854A CN200980140585A CN102176819A CN 102176819 A CN102176819 A CN 102176819A CN 2009801405854 A CN2009801405854 A CN 2009801405854A CN 200980140585 A CN200980140585 A CN 200980140585A CN 102176819 A CN102176819 A CN 102176819A
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vitamin
anticoagulant
analogues
composition
concentration
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斯特凡·恩德波尔斯
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Bayer CropScience AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/002—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits
    • A01N25/004—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits rodenticidal
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Food Science & Technology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fodder In General (AREA)

Abstract

The present invention relates to the combination of an anticoagulant rodenticidal active substance and an analog of vitamin D, wherein at least one of the two components is used in a very low concentration.

Description

The synergy rodenticide
The combination that the present invention relates to novel vitamin D analogues and anticoagulant is used for rodent control composition with low concentration.
From the 1950's, just use anticoagulant, particularly the Hydroxycoumarin class is killed the rodent compound as the activity that is used for preventing and treating rodentine bait and other compositions.These reactive compounds show the activity of enzyme vitamin K epoxide reductase, and its vitamin K with oxidation is transformed into its activity form, i.e. the vitamin K quinhydrones.This form of vitamin K is that gamma-carboxylation is required.Therefore the shortage of the activity form of vitamin K causes comprising the carboxylation deficiency of the multiple proteins of Stuart factor.This has destroyed the step of the prothrombin in the coagulation cascade to the conversion of fibrin ferment, and this and then the animal that may cause having absorbed the coumarin of corresponding dosage become weak and may be dead.The 1st generation Hydroxycoumarin be used for bait with 0.02% to 0.06% concentration (unless otherwise noted, otherwise always being expressed as weight %) usually, the Hydroxycoumarin in the 2nd generation uses with 0.0025% or 0.005% concentration.
Another group is the vitamin D of two kinds of forms as the reactive compound of rodenticide, i.e. ergocalciferol and Vitamin D3 (vitamin D 2And D 3).The vitamin of crossing multiple dose produces hypercalcinemia.Under this situation, calcium absorbs from food to the degree that increases by intestines, and reuptakes from bone salts.High calcium concentration causes atherosis (Sklerotisierung) of soft tissue in the blood flow that is caused, and cardiovascular system is had destructive effects.Calciferol is used for bait with 0.1% to 0.6% concentration usually.
From this reactive compound of two groups also in killing the rodent bait, mutually combine (GB 1 371 135).Mixture (Greaves, the J.H. of reactive compound have also been described in other places; Redfern, R.; King, R.E. (1974), J.Hyg.Cambridge 73,341-351 or Kerins, G.M.; Endepols, S.; MacNicoll, A.D. (2002), Comp.Clin.Path.11,59-64).The seventies in 20th century to the nineties, introduced the product of the combination (0.025%+0.1%) that contains anticoagulant warfarin (warfarin) and ergocalciferol or anticoagulant warfarin (coumatetralyl) and the combination (0.0375%+0.025%) of Vitamin D3 on the market.
Along with introduction the 2nd generation Hydroxycoumarin in the worldwide, the product that the combinations thereof product is contained the reactive compound of these renewals replaces.But this combination product is not accepted, and this is because calciferol causes timid bait (bait shyness) and reduces bait to rodentine attraction (Prescott, C.V. under used concentration; El-Amin, M.; Smith, R.H. (1992): Calciferols and bait shyness in the laboratory rat.Proc.15 ThVertebrate Pest Conf., Univ.Calif., Davis, 218-223).Use the not showing one's usefulness property of calciferol of low concentration, this is because compare with the anticoagulant of no calciferol, can not guarantee active abundant raising.
In the feeding test that utilizes rat and mouse, find that in the animal of some strain even when two kinds of reactive compounds use with the concentration that is lower than common employing, more than combination has good unexpectedly activity.The surprising fact is that the concentration of one of two kinds of reactive compounds in fact can significantly be brought down below typical concentration, that is, and and Vitamin D3 0.01% or 0.005% level only for example.Even near the minimum of a value of the amount of two kinds of reactive compounds disclosed concentration range in GB 1 371 135, also find good activity.This can't expect, is for example 0.1% to exist with higher relatively concentration because one of disclose among the embodiment that provides among the GB 1 371 135 in two kinds of components at least.Therefore, those skilled in the art can't be expected at truly and implement disclosed instruction among the GB 1 371 135 in the extreme lower range.
A surprising especially fact is, the amount of one of two kinds of combined activity compounds even can further reduce on concentration promptly, significantly is lower than Cmin claimed among the GB 1 371 135.Thereby, can be by this way in conjunction with reactive compound coumatetralyl (the 1st generation Hydroxycoumarin) and Vitamin D3 (vitamin D 3), make one of two kinds of reactive compounds only be present in the bait, and demonstrate especially good activity with 0.0025%.This concentration is equivalent to only be 50% of Cmin claimed in the above-mentioned patent.
Although GB 1 371 135 claimed concentration all surpass 0.005% in each case, same as indicated in the embodiment, only under obviously higher concentration, just demonstrate rational activity.Therefore, expectability even 0.0025% concentration can not demonstrate synergistic effect, particularly under the situation of the insensitive wild strain of home mouse (house mouse (Mus musculus)) and brown rat (Rattus norvegicus (Rattus norvegicus)).
The present invention relates to the combination that at least a active anticoagulation kills the analog of rodent (for example muroid) compound and vitamin D, use one of at least in two kinds of components with low-down concentration (being equal to or less than 0.0049%).
Anticoagulant is the compound that is selected from indandione derivative or Hydroxycoumarin class (the 1st generation and the 2nd generation) in the present invention.These materials in worldwide, be used to prevent and treat rodent (referring to, for example DE 2506769; JP 48023942; CH 481580; Paposci (1974): the 155th page of Beihefte Z.Angew.Zool. and DE 2506769).The 1st generation the anticoagulant material example comprise 4 hydroxy coumarin derivative (1-phenyl-2-acetyl group)-3-ethyl-4 hydroxy coumarin (" warfarin "); 3-(α-acetonyl-4-chloro benzyl)-4 hydroxy coumarin (" coumaran (coumachlore) "); 3-(1 '; 2 '; 3 '; 4 '-tetrahydrochysene-1 '-naphthyl)-4 hydroxy coumarin (" coumatetralyl "); and indandione derivative; as 1; 1-diphenyl-2-acetyl group indane-1; 3-diketone (" diphacinone (diphacinone) ") and (1 '-right-chlorphenyl-1 '-phenyl)-2-acetyl group indane-1,3-diketone (" chloradion (chlorodiphacinone) ").In the 2nd generation, comprised following: 3-[3-(4 '-hydroxyl-3 '-the coumarin base)-3-phenyl-1-(4 '-bromo-4 '-xenyl) third-1-alcohol (" Bromadiolone (bromadiolone) "), 3-(3 '-to xenyl-1 ', 2 ', 3 ', 4 '-tetrahydrochysene-1 '-naphthyl)-4 hydroxy coumarin (" difenacoum (difenacoum) "), 3-[3-4 '-bromo biphenyl base-4-yl)-1,2,3,4-tetrahydrochysene-1-naphthyl]-4 hydroxy coumarin (" Brodifacoum (brodifacoum) "), 4-hydroxyl-3-[1,2,3,4-tetrahydrochysene-3-[4-(4-trifluoromethyl benzyloxy) phenyl]-the 1-naphthyl] coumarin (" flocoumafen (flocoumafen) "), and hydroxyl-4-benzothiopyran derivative ketone, for example " thiophene mouse ketone (difethialone) ".
Other anticoagulants that are applicable to preparation bait of the present invention comprise methyl substituted benzhydryl ketone of following 2-azacycloalkyl and benzhydryl methyl alcohol class: 1-phenyl-3-(2-piperidyl)-1-(p-methylphenyl)-2-acetone, 3,3-diphenyl-1-(2-pyrrolidinyl)-2 pentanone, 1,1-diphenyl-3-[2-(six hydrogen-1H-azepine Base)]-2-acetone, 1-(4-fluorophenyl)-1-phenyl-3-(2-piperidyl)-2-acetone, 1-(4-methylbenzene sulfenyl)-1-phenyl-3-(5,5-dimethyl-2-pyrrolidinyl)-and 2-acetone, 1-(to coumenyl)-1-phenyl-3-(the 4-tert-butyl group-2-piperidyl)-2-acetone, 3,3-diphenyl-1-[2-(six hydrogen-1H-azepine
Figure BPA00001347640800032
Base]-2-butanone, 3-(2, the 4-dichlorophenyl)-3-phenyl-1-(2-piperidyl)-2-heptanone, 1,1-diphenyl-3-(5-methyl-2-pyrrolidinyl)-2-acetone, 3,3-diphenyl-1-(2-piperidyl)-2-butanone, α-(Alpha-Methyl-α-phenylbenzyl)-2-piperidines ethanol, α-(α-ethyl-α-phenylbenzyl)-2-pyrrolidines ethanol, (2,5-dimethyl-α-phenylbenzyl)-2-piperidines ethanol and α-(diphenyl methyl)-2-(six hydrogen-1H-azepine
Figure BPA00001347640800033
) ethanol and salt (being described among the DT-OS 2 417 783) thereof, and 4 '-(fluorophenyl)-2-(2-pyrrolidinyl) acetophenone, 4 '-phenyl-2-(5,5-dimethyl-2-pyrrolidinyl)-acetophenone, 4 '-[to (trifluoromethyl) phenyl]-2-(2-piperidyl) acetophenone, 4 '-(to butoxy phenyl)-2-(the 4-tert-butyl group-2-piperidyl) acetophenone, 2 '-phenoxy group-2-(2-piperidyl) acetophenone, 4 '-(to fluorophenoxy)-2-(5,5-dimethyl-2-pyrrolidinyl) acetophenone, 4 '-(to chlorophenoxy)-2-(2-piperidyl) acetophenone, 4 '-[-(trifluoromethyl) phenoxy group]-2-(2-piperidyl) acetophenone, 4 '-(to the phenoxy butoxy base)-2-(2-pyrrolidinyl) acetophenone, 2-(2-piperidyl)-4 '-(trans-the p-methylphenyl ethenylidene) acetophenone, 2-(2-six hydrogen-1H-azepine
Figure BPA00001347640800034
Basic)-4 '-(trans-styryl) acetophenone, 4 '-(-the methoxyphenyl ethenylidene)-2-(2-pyrrolidinyl) acetophenone, 2-(2-piperidyl)-4 '-[(to methyl mercapto) phenyl-ethenylidene] acetophenone, 4 '-(3-phenoxy group propoxyl group)-2-(2-piperidyl) acetophenone, 4 '-(4-phenyl butyl)-2-(2-piperidyl) acetophenone, 4 '-(α, α-Er Jiajibianji)-2-(piperidyl) acetophenone, 4 '-phenethyl-2-(3,5-diethyl-2-piperidyl) acetophenone, 4 '-phenyl-2-(2-pyrrolidinyl) acetophenone, α-[2-(2-phenyl ethoxy) phenyl]-2-piperidines ethanol, α-(to Phenoxyphenyl)-2-pyrrolidines ethanol, α-[4-(4-bromine phenoxy group) phenyl]-6-methyl-2-piperidines ethanol, α-(to phenethyl) phenyl-2-pyrrolidines ethanol, α-to xenyl-2-six hydrogen-1H-azepine
Figure BPA00001347640800035
Ethanol, α-[3-(4-phenoxy group butoxy) phenyl]-2-piperidines ethanol and α-(4-benzyl) phenyl-2-piperidines ethanol and salt (referring to DE-A-2 418 480) thereof.
Following rare earth metal salt can be used as anticoagulant equally: dihydroxy benzenes disulfonic acid two neodymiums (Acta physiol.Acad.Sci.Hungar.24,373), 3-sulfonic group pyridine-4-carboxylic acid two neodymiums and three (4-aminobenzenesulfonic acid) ceriums (III).
The preferred anticoagulant of the present invention be the 1st generation anticoagulant warfarin, coumatetralyl, chloradion and diphacinone and the 2nd generation anticoagulant such as Bromadiolone, difenacoum, Brodifacoum, flocoumafen and thiophene mouse ketone.
Novel vitamin D analogues is ergocalciferol and Vitamin D3 in the present invention.They are 3 beta-hydroxies-Δs 5, the derivative of the steroids of 7-17 β-replacement.Calciferol is formed by irradiation by ergosterol.In addition, other analogs of vitamin D and metabolite also are fit to, for example hydroxy cholecalciferol, dihydroxy Vitamin D3, HEC and dihydroxy ergocalciferol.Preferred ergocalciferol and Vitamin D3.
In composition of the present invention, also can there be two or more anticoagulants and/or novel vitamin D analogues (in this case, concentration value is applicable to the total amount of anticoagulant and novel vitamin D analogues respectively).
In composition of the present invention, anticoagulant or novel vitamin D analogues are being equal to or less than 0.0049% at least, and be preferred 0.001% to 0.0045%, more preferably 0.002% to 0.004%, and very preferably 0.0025% to 0.0035% concentration exists.
At anticoagulant with at the most 0.0049%, preferred 0.001% to 0.0045%, more preferably 0.002% to 0.004%, very preferably 0.0025% to 0.003% when being present in the composition of the present invention, and novel vitamin D analogues can exist with 0.005% to 1.0% as usual.
At novel vitamin D analogues with at the most 0.0049%, preferred 0.001% to 0.0045%, more preferably 0.002% to 0.004%, very preferably 0.0025% to 0.0035% when being present in the composition of the present invention, and anticoagulant can exist with 0.005% to 1.0% as usual.
In another embodiment, in composition of the present invention, anticoagulant and novel vitamin D analogues all with at the most 0.0049%, preferred 0.001% to 0.0049%, more preferably 0.001% to 0.0045%, very preferably 0.002% to 0.004%, preferred especially 0.025% to 0.0035% exists.
Below combination is the example of the particularly suitable combination of anticoagulant and novel vitamin D analogues:
A) coumatetralyl and Vitamin D3
B) coumatetralyl and ergocalciferol
C) chloradion and Vitamin D3
D) chloradion and ergocalciferol
Below combination is the particularly suitable combination of anticoagulant and novel vitamin D analogues and the example of concentration value:
A) anticoagulant (0.001% to 0.0049%)+ergocalciferol/Vitamin D3 (0.005% to 0.5%);
B) anticoagulant (0.005% to 0.1%)+ergocalciferol/Vitamin D3 (0.001% to 0.0049%);
C) anticoagulant (0.001% to 0.0049%)+ergocalciferol/Vitamin D3 (0.001% to 0.0049%);
Below combination is the example of suitable concentration of the reactive compound combination of coumatetralyl+Vitamin D3:
A) coumatetralyl (0.0025%)+Vitamin D3 (0.025%);
B) coumatetralyl (0.0375%)+Vitamin D3 (0.0025%);
C) coumatetralyl (0.004%)+Vitamin D3 (0.004%);
The rodent control composition that kills among the present invention is all types of rodent baits that kill.They are fully known in the prior art.Recommendation is based on those of cereal such as oats flakes, wheat, corn etc.They can be to contain the dumpable bait that one or more plant the cereal compositions, extrude bait such as particle or pill, wax stone, based on the mixture of the soft or pasty state of plant fat and meals, or based on the gel of oily preparation or aqueous compositions.Especially the recommendable pasty state bait of forming by cereal or meals and plant fat.Most suitable example comprises the pasty state bait of 10g to 200g packing.
Other administration form is the drink of liquid or gelation, and so-called contact composition such as powder and foam.These compositions are not baits, but send with adhere to rodentine fur and only resonable when hair through port take in.
Composition of the present invention is suitable for controlling the pest rodent of all kinds, comprises representational Microtus (Microtus), paddy field Mustella (Arvicola), Genus rattus (Rattus) and Mus (Mus).In the area of human living, it should be noted that home mouse (house mouse) especially, house mouse (Mus musculus/domesticus), brown rat, Rattus norvegicus (Rattus norvegicus), and egyptian rat, home mouse (house rat) or black mouse, rattus rattus (R.rattus).Can on open soil, use,, comprise that use is the same in animal corral, storage and Production Regional and the sewerage system as at building.
Embodiment
1) bait has the anticoagulant coumatetralyl (0.0375% w/w) and the novel vitamin D analogues Vitamin D3 (0.0025% w/w) of conventional concentration based on whole wheat.House mouse (Mus musculus domesticus) with wild strain is tested said composition in 5 days feeding test.Lethality is 95% (n=20).
2) bait has anticoagulant coumatetralyl (0.0045% w/w) and novel vitamin D analogues Vitamin D3 (0.005% w/w) based on whole wheat.Rattus norvegicus (Rattus norvegicus) with wild strain is tested said composition in 4 days feeding test.Lethality is 100% (n=12).
3) bait has anticoagulant coumatetralyl (0.0025% w/w) and novel vitamin D analogues Vitamin D3 (0.01% w/w) based on whole wheat.Rattus norvegicus (Rattus norvegicus) with wild strain is tested said composition in 4 days feeding test.Lethality is 100% (n=12).

Claims (10)

1. one kind is used to control rodentine composition, comprises at least a anticoagulant and at least a novel vitamin D analogues, and wherein at least a component exists with the ratio that is no more than 0.0049 weight %.
2. composition according to claim 1, wherein said anticoagulant are Hydroxycoumarin or indandione derivative.
3. composition according to claim 1, wherein said novel vitamin D analogues is selected from ergocalciferol and Vitamin D3.
4. according to each described composition in the claim 1 to 3, the content of wherein said anticoagulant is for being no more than 0.0049 weight %.
5. according to each described composition in the claim 1 to 3, the content of wherein said novel vitamin D analogues is for being no more than 0.0049 weight %.
6. according to each described composition in the claim 1 to 5, the content of wherein said anticoagulant and the content of described novel vitamin D analogues are for being no more than 0.0049 weight %.
7. according to each described composition in the claim 1 to 3, wherein said anticoagulant exists with 0.001% to 0.0045% amount, and described novel vitamin D analogues exists with 0.005% to 1.0% amount.
8. according to each described composition in the claim 1 to 3, wherein said novel vitamin D analogues exists with 0.001% to 0.0045% amount, and described anticoagulant exists with 0.005% to 1.0% amount.
9. composition according to claim 6, the amount of wherein said anticoagulant and described novel vitamin D analogues are 0.001% to 0.0049%.
10. according to each described composition in the claim 1 to 9, it is in the form of rodent bait.
CN2009801405854A 2008-10-14 2009-10-07 Synergistic rodenticidal agent Pending CN102176819A (en)

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JP2012505259A (en) 2012-03-01
WO2010043322A1 (en) 2010-04-22
EP2343972A1 (en) 2011-07-20
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AU2009304313A1 (en) 2010-04-22
BRPI0920208A2 (en) 2015-08-18

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